Failure of free energy relation under non-Markovian heat bath temperature change

We investigate the free energy relation for a system contacting with a non-Markovian heat bath and find that the validity of the relation sensitively depends on the non-Markovian memory effect, which is especially related to the initial preparation effect. This memory effect drives the statistical distribution of the system out of the initial preparation, even if the system starts from an equilibrium state. This leads to the violation of the free energy relation. A possible way of eliminating this memory effect is proposed.     

Understanding the optical spectroscopy of amphiphilic molecular rectifiers: a density functional approach

We present results of first principles density functional theory calculations of the electronic and atomic structural properties of model Z-type Langmuir-Blodgett (LB) layers comprising amphiphilic quinolinium tricyanoquinodimethanide (Q3CNQ) chromophores. We find that the chromophore electronic ground state is not as clearly "zwitterionic" as required by models to explain electrical rectification purportedly seen in such systems. The computed visible region transitions are not what have been assumed to be the intervalence charge transfer bands seen in the visible region of molecules in Z-type LB films. Our own LB deposition and spectroscopic studies suggest that almost all visible region features previously seen may be ascribed to aggregates. The calculated lowest energy electronic excitation between HOMO and LUMO levels, which is located in the near infrared region, has a transition moment aligned approximately 9° off the molecular long axis, and has a normalized oscillator strength of 1 order of magnitude higher than those of the visible region transitions. This most dominant feature has been neglected from discussions of Langmuir-Blodgett layer rectification but our own deposition studies show no sign of this feature, indicating that the structure of the modeled system differs from that of typical experimental structures. The model indicates that such idealized LB layer structures cannot confidently be invoked to explain their experimental optical or electrical properties.     

Characterization of Major and Minor Organic Pollutants in Wastewaters from Coal Gasification Processes

Abstract

In order to investigate the feasibility of anaerobic biological treatment for wastewaters generated from thermal gasification processes of coal, a characterization program was implemented whose major effort consisted in the elucidation of specific organic constituents contained in the wastewater. Solvent extraction in acid and base conditions followed by glass capillary gas chromatography in combination with several detectors (i.e., FID, NPD, and MS-DS) were employed for the investigation of major and minor “extractable” organic constituents. Direct aqueous injection on a polar glass capillary column (i.e., OV-351) was used for the major “nonsolvent extractable” organic constituents amenable to GC. The identity of 28 organic compounds was confirmed by comparison with pure standards. Phenol, the three cresol isomers, 5,5-dimethyl-hydantoin and 5-methyl,5-ethylhydantoin were identified as major wastewater constituents. Several substituted phenols (e.g., methyl, dimethyl, trimethyl, methylethyl, hydroxy and methoxy), pyridines, anilines, quinolines, PAHs, dibenzofuran and aldehydes were either confirmed or tentatively identified as minor wastewater constituents. Although the organics identified did not account for the total organic content, which implies the presence of still unidentified highly polar compounds, the information was utilized to set a data base for monitoring the biological treatment operations. Process monitoring data indicated that several organics (i.e., 5,5-dimethyl-hydantoin, 5-methyl,5-ethylhydantoin, o-cresol, m-cresol and p-cresol) were only partially removed by the treatment process employed.     

Oblique Bounce of a Rubber Ball

Measurements are presented on the oblique impact of a hollow rubber ball incident on a polished granite surface, and the results are compared with those for a solid rubber superball. The hollow ball had a much higher coefficient of sliding friction than the superball, resulting in significant differences in all bounce parameters, at all angles of incidence. The hollow ball gripped the surface at all observed angles of incidence, resulting in one or two reversals in the direction of the friction force during the impact. The friction force was measured directly, as was the rotation speed of the ball during the impact. The results show that the tangential coefficient of restitution of a ball depends on both the coefficient of sliding friction and the ratio of the tangential to the normal vibration frequency of the ball.     

Direct detection and quantitation of He@C60 by ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry

In this paper, we report negative ion microelectrospray Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry of C60 samples containing approximately 1% 3He@C60 or 4He@C60. Resolving He@C60- and 4He@C60- from C60 containing 3 or 4 13C instead of 12C atoms is technically challenging, because the target species are present in low relative abundance and are very close in mass. Nevertheless, we achieve baseline resolution of 3He@C60- from 13C3(12C57-) and 4He@C60- from 13C4(12C56-) in single-scan mass spectra obtained in broadband mode without preisolation of the ions of interest. The results constitute the first direct mass spectrometric observation of endohedral helium in a fullerene sample at this (low) level of incorporation. The results also demonstrate the feasibility of determining the extent of He incorporation from the FT-ICR mass spectral peak heights. The present measurements are in agreement with those obtained by the pyrolysis method [1-3]. Although limited in sensitivity, the mass spectral method is faster and easier than pyrolysis.